JPS61293227A - Production of s-triazine ring-containing soluble polyimidesiloxane precursor - Google Patents

Abstract

PURPOSE:To obtain the title precursor excellent in workability, storage stability and adhesiveness, by reacting a tetracarboxylic acid dianhydride with a guanamine, a diamine and an aminosilicon compound and reacting the product with a silylating agent. CONSTITUTION:A mol of tetracarboxylic acid dianhydride of formula I, B mol of a guanamine of formula II, E mol of a diamine of formula III and D mol of an aminosilicon compound are prepared in such amounts that the relationships V, VI and VII may hold among A, B, E and D. These compounds are reacted with each other at 0-60 deg.C for 0.2-6hr in the presence of a solvent. A silylating agent of formula IX in an amount of F mol in the range represented by the formula VIII is added to the reaction system and he mixture is reacted at 60-20 deg.C for 0.5-30hr to obtain the purpose precursor of an intrinsic viscisity as measured in a solvent at 30+ or -0.01 deg.C and a concentration of 0.5wt% of 0.05-5g/dl. In the formulas, R<1> is a tetravalent carbocyclic aromatic group, R2 is a 2-12C aliphatic group or the like, R<6> is -(CH2)8- or the like, R<7>, R<11>, R<12> and R<13> are each a 1-6C alkyl, etc., X<1> and X<2> are each alkoxy or the like and 1<=k<=3.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a novel precursor of polyimidosiloxane having an 8-triazine ring.

[Conventional technology and problems]

Conventionally, polyimide resins have been widely used as protective materials, insulating materials, adhesive materials, films, and structural materials in the field of electronic equipment, mainly from the viewpoint of heat resistance. In many cases, the method of using it is to apply it to the target object as a precursor before becoming a cyclized polymer, and then bake it to complete imidization and crosslink it. Various proposals have been made to improve the functions and effects. However, such conventional techniques cannot necessarily fully satisfy the current diversified, individualized, and sophisticated needs.

For example, polyamic acid, which has been conventionally used as a polyimide precursor for electronic materials, is cured by applying a solution thereof to a substrate and imidizing it, but there are various disadvantages in its use as described below. That is, the temperature during firing is 300 to 400
℃, which may exceed the heat resistance temperature of the base material, insufficient adhesion to the silicone coating target, and poor stability over time during storage. There was a problem.

Many copolymers with silicon compounds have been proposed to improve the adhesion of the above-mentioned problems. For example, JP-A-57-143328, JP-A-58-7473, and JP-A-58-. No. 13631 proposes a technique for producing a polyimide-siloxane copolymer using a polyimide precursor obtained by replacing a part of the diamine component as a raw material with polysilogysane terminated at both ends with diamine. However, in this case, although a certain degree of improvement in adhesion was observed, there was a problem in that as the siloxane content in the copolymer increased, the degree of polymerization decreased and the ability to form a coating decreased.

Also, Special Publication No. 58-32], No. 62 and Special Publication No. 58
-32163, a suitable carboxylic acid derivative such as tetracarboxylic dianhydride is reacted with a diamine to form a polyamide carboxylic acid having a terminal group such as an acid anhydride, and then this polyamide carboxylic acid and aminocricon A silicon-containing polyamide carboxylic acid prepolymer is obtained by reacting the silicon-containing polyamide carboxylic acid prepolymer with a compound at -20"C to +50°C, and the prepolymer is either left unimidized or imidized in the presence of a dehydrating agent. Under mild conditions (low temperature preferably below 50°C, especially -20°C to +
Chemically cyclize (imidize) at 25°C) to obtain an organosilicon carbonaceous polyimide precursor, and heat this precursor in solution in the presence or absence of silane diol or siloxane diol to form imide. A technique for crosslinking the polyimide siloxane upon completion of the chemical reaction is disclosed. However, in order to imidize this polyimide siloxane precursor, which is similar to conventional polyimide precursors whose main component is polyamide carboxylic acid, the polyimide siloxane precursor is
It requires firing at a high temperature reaching 0°C, and if the obtained cyclized precursor has a high silicon content, it has poor coating film forming ability.
If the silicon content is low, the adhesion to silicon wafers and glass will be poor, and when producing pre-imidized polyimide siloxane precursors, cyclization by low-temperature treatment in the presence of a dehydrating agent will take a long time, making it difficult to actually On the contrary, if the cyclization is accelerated by heating, the entire solution becomes gelatinous and fluidity is completely lost.

Furthermore, in general, when the polymer contained in polyamide foam is polyamic acid, the viscosity decreases over time.
On the contrary, in the case of No. 3 etc., the viscosity increases over time and the storage stability is poor.

As mentioned above, there are various problems with the conventional technology. It has a moderate viscosity and provides good workability, can be baked and cured at relatively low temperatures and in a short time, has good film forming ability, has excellent storage stability, and has good adhesion to silicon wafers, glass, etc. There was a demand for the development of a precursor that would give a polyimide resin with good properties.

Means for Solving Problem C] The present invention is a means for solving the problems of the above-mentioned prior art and satisfying the above-mentioned needs, and is a means for solving the above-mentioned problems of the prior art, and is a means for solving the above-mentioned problems of the prior art. mole, guanamine B mole represented by formula (2), diamine E mole represented by formula (3), and amine silicon compound D mole represented by formula (4)"iA, B.

The relationships of formula (5), formula (6), and formula (7) are made to exist between E and D, and 0.
After carrying out the reaction for 2 to 6 hours, F mole of the silylating agent represented by the formula (9) in the range shown by the formula (8) is added, and 0.5 By reacting for ~30 hours, the temperature in the solvent was 30±0.01℃1.
Intrinsic viscosity 0.05-5y measured at a concentration of 0.5% by weight
This is a method for producing an imidized soluble polyimide siloxane precursor having a 7rtt s-) riazine ring.

R" NH, -R2-NH, ... (3) NHt-R'-
8iR'g-kX' @ j + $ 1 (4) 2A
Straw 2B+2E10D... (7) 0≦"
2≦1 ...self (8) k R11R11ilR13SiX2 ......(
9) c In formulas (1) to (4) and (9), Rt represents a tetravalent carbocyclic aromatic group, R2 is an aliphatic group having 2 to 12 carbon atoms, and 4 to 30 carbon atoms. alicyclic group, carbon number 6~
Represents 30 aromatic aliphatic groups, carbocyclic aromatic groups having 6 to 30 carbon atoms, or the following formula
ntqo y or -6 (however, 3 here is 1 to
Indicates an integer of 4. ), R3 and R4 independently have 1 to 1 carbon atoms
represents an alkyl group of 6, a phenyl group, or an alkyl substituted phenyl group having 7 to 12 carbon atoms, and t takes a value of 1≦t≦100. ), R6 is +CH1+-1+ independently of R9
Cn, 入(n, +CHtqOfl or in (however, S indicates an integer from 1 to 4), R7, R口, R12
and R13 independently represent an alkyl group having 1 to 6 carbon atoms, a heptadyl group, or an alkyl-substituted phenyl group having 7 to 12 carbon atoms, and 11G is an aliphatic group having 8 or less carbon atoms, an araliphatic group, or hydrogen. , Xl and X2 independently represent an alkoxy group, an acetoxy group, a halogen or a hydroxyl group, and k takes a value of 1≦3. ] The raw materials of the present invention will be explained.

Examples of the tetracarboxylic dianhydride represented by formula (1) include the following compounds.

Pyromellitic dianhydride, 3.3', 4.4'-biphenyltetracarboxylic dianhydride, 2.2'.

3.31-biphenyltetracarboxylic dianhydride, 2,
3.3',4'-biphenyltetracarboxylic acid dill
l hydrate, 3.3', 4.4'-benzophenonetetracarboxylic dianhydride, 2.3.3', 4'-benzophenone/tetracarboxylic dianhydride, 2°2', 3.3'
-benzopheno/tetracarboxylic dianhydride, bis(3
, 4-dicarboxyphal)-ether dianhydride, bis(3,4-dicarboxyphal)-sulfone dianhydride, 1°2.5.6-naphthalenetetracarboxylic dianhydride, 2,3,6.7 - Naphthalene tetracarboxylic dianhydride, etc.

Moreover, the following compounds can be mentioned as specific examples of guanamines represented by formula (2).

Guanamine, methylguanamine, ethylguanamine, propylguanamine, benzoguanamine, toluylguanamine, etc.

Next, examples of the diamine represented by the general formula (3) include the following compounds.

4, s'-diaminodiphenyl ether, 4゜4'-diaminodiphenylmethane, 4.4'-diaminodiphenylsulfone, 4.4'-diaminodiphenyl sulfide, 4.4'-diaminodiphenyl thioether, 4.4
'-Di(meta-aminophenoxy)diphenylsulfone, 4,4'-di(hala-aminophenoxy)diphenylsulfone, ortho-phenylene/cyamine, metaphenylenediamine, paraphenylenediamine, benzidine, 2
．． 2'-diaminobenzophenone, 4゜4'-diaminobenzophenone, 4.4'-diaminodiphenyl-2,
2'-propane, 1.5-diaminonaphthalene, 1.8
- Aromatic diamines such as diaminonaphthalene, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, 4,4-dimethylhebutamethylene diamine,
2. Aliphatic diamines such as 11-dodecanediamine, silicone diamines such as bis(p-aminophenoxy)dimethyl 7rane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, 1,4-diaminocyclohexane, etc. Aminoalkyl-substituted aromatic compounds such as alicyclic diamine, 0-xylylene diamine, m-xylylene diamine, etc.

Further, the following compounds can be mentioned as diaminopolysiloxanes represented by 2〇ll.

CH8CH.

OH, CH.

CH3CH.

C*Hs　　C,H.

Next, examples of the aminocricone compound represented by formula (4) include the following compounds.

NHt+CHthSi(OCHs)s−NHzfCHt
kSl(OCtHs)s, NHt+ CHt+rSi(
CHs ) (0CHs )t, NH, (-CHt+!
-8i(CHtX0CtHs)t, MHI%C
H@%Si(c,H,)(On -CBHI)t
5NHt”G CHt*5i(OCH3)3,NH,(
CH, Ant (OCIHs) 1 sNH, 1,000H*+r
Si(CHaX0CtHs)t,NH,Cn5i
(OCHs)s, h(n5i(OCtHs)s, NH,
(Si (CHa) (OCHs)t, NHt
(Si(CHa)(OCtHs)t,NHl
CFCHt + Si (OCHs)s, NH, -◎
HCH, juice Si(OCtHg)s, etc.

Moreover, the following compounds can be mentioned as the silylating agent represented by formula (9).

(CHs) ssi(0CHs), (Cxin)ssi(
OCtHs), (CHs)sSi(On-CsHy)s
, (CHs)t(CtHI)Si(OCH8), (CH
sMCJIs)Sl(OCtHg), (CHs)asi
Oh.

(CHs)ssi (OCOCR,), N
-Methyl-'2-pyrrolidone, dimethylacetamide,
Dimethylformamide, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylphosphoramide, methylformamide, N-acetyl-2-pyrrolidone, toluene, xylene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol One or more types of dimethyl ether, cyclopentanone, cyclohexanone, etc. can be used, and the above solvent t
It can also be used as a mixed solvent with other solvents containing 1-30% by weight or more.

(Reaction method) Next, the reaction method will be explained. A mole of tetracarboxylic dianhydride represented by formula (1), B mole of guanamine represented by formula (2), 8 mole of diamine represented by formula (3) mol and D mol of an aminocricon compound represented by formula (4) in a reaction solvent.At this time, A, B, E and D have formula (5), formula (6) and approximately formula (7) between them. )
It is determined that the following relationship exists. Formula (5) defines the range in which the obtained soluble polyimide siloxane precursor can maintain good adhesion to silicon wafers and glass when used as a surface protective film for semiconductors, and also has good film formability and mechanical properties. This defines the range within which strength can be maintained.

Formula (6) defines the range of the amount necessary for imparting the physical characteristics to the soluble polyimidosiloxane precursor when it has an 8-triazine ring.

Formula (7) is a relational formula when all the amino groups in guanamines, diami/aminocricone compounds, and all of the acid anhydride in the tetracarboxylic dianhydride are reacted in equivalent amounts, but it is not necessarily accurate. It does not have to be equivalent to, for example, A
If the number of moles is within the range of ±10% of the number of moles determined by formula (7), the precursor aimed at by the present invention can be obtained. "Habo"
means this.

In the method of the present invention, the reaction of each raw material in a solvent is carried out in the first step, in which tetracarboxylic dianhydride is reacted with guanamines, diamines, and aminosilylon compounds at a relatively low temperature; After the completion of the reaction, the reaction solution (hereinafter sometimes referred to as the first-stage reaction completion solution) is heated at a relatively high temperature in the presence of a silylating agent to react with at least the water generated at that time. This is done by

It is preferable that the amount of the reaction solvent used be 60% by weight or more based on the total amount of the reaction solvent and the raw materials added to it at the time of the reaction in each of the above steps, since this facilitates the stirring operation.
It is not necessary to use more than t amount %.

The first stage reaction is carried out in the presence of the above-mentioned reaction solvent at 0°C or higher at 6°C.
0°C), preferably at a temperature of 5°C or above and 40'O>A for 0.2 to 6 hours. Specifically, it is possible to synthesize a random copolymer by adding all of the tetracarboxylic dianhydride, guanamines, diamines, and aminocricone compounds to the reaction solvent at the same time and reacting them, but the order of addition is selected. In particular, it is also possible to synthesize copolymers with a more block-like structure. In this case, there is no particular restriction on the order in which the four raw materials are added, but it is easier to obtain a polymer with a higher molecular weight if the amine silicon compound is added last in the first reaction step. In this first stage reaction, the above four raw materials are dissolved in the solvent and the reaction progresses relatively quickly, and when a homogeneous and transparent reaction liquid is produced, the reaction is almost complete, but it will continue for a while. It is preferred to ensure completion of the reaction. The main reaction is the production of polyamide carboxylic acid (hereinafter sometimes referred to as intermediate G) having an aminocricone compound bonded to both ends, as described later.

The second stage reaction is carried out by the formula (8
) In the presence of a silylating agent represented by the formula (9) with F moles in the range, the reaction temperature is further increased from the first stage reaction temperature to 0.5 to 200°C at a temperature of 60°C to 200°C. 3
This is a reaction in which the mixture is heated for 0 hours, and the water generated at that time is reacted with an amount of water effective for hydrolyzing Xi of the amine silicon compound at the terminal of intermediate G and X2 of the silylating agent. The silylating agent may be added at the start of the second stage reaction, but it may also be added in advance together with other raw materials before the first stage reaction begins. This is preferable because it has no substantial effect on the reaction and facilitates the operation of transferring the reaction from the first stage to the second stage. As the proportion of guanamines in the raw material increases, or as the value of k in formula (4) decreases, the second stage reaction can be carried out by adding less silylating agent. As described later, the main reaction in the second stage reaction is to cyclize and imidize the amide carboxylic acid part of intermediate G produced in the first stage reaction, and to form the terminal of intermediate G. Xl of the aminocricon compound and X2 of the free silylating agent
More than half of the hydrolyzable groups, i.e., alkoxy groups, acetoxy groups, or halogens, are hydrolyzed and converted to hydroxyl groups (X'' may be -OH from the beginning)
and, at least in part, the intermediates G and the intermediate G
and the silylating agent, or between the hydroxyl groups bonded to 81 between the silylating agents, or between the hydroxyl group and the hydrolyzable group, a condensation reaction occurs to form a siloxane bond (hereinafter sometimes referred to as a siloxane condensation reaction) )It is to be. In the above siloxane condensation between the silylating agents, the silylating agent simply becomes an inert compound and dissolves in the reaction solvent, but other siloxane condensations are formed at the Xl and Xl positions. In addition, when this precursor is fired, it is preferable that siloxane bonds are finally generated at all or close to the Xl and X2 positions of Sl, and therefore 1/2 to all of Xl and X2 are hydrolyzed. It is preferable to generate 10H. The maximum amount of water effective for such hydrolysis, that is, the amount of water consumed to hydrolyze all of Xl and ). The amount of water consumed in the above hydrolysis
At least a portion of this is covered by water generated when polyamic acid is imidized.

If the imidization rate is a%, the amount of water generated is 2AX a
X 1/100 mol. Therefore, in the second stage reaction, the amount of water added at the end of the IEI stage reaction is ([(
DXk+F)X1/2~(DXk+F))-2AXaX
1/100) mole, but if the water contained in the reaction solvent used cannot be ignored, this water content must also be taken into account. As described above, the amount of water that needs to be added in the second step reaction varies depending on the amount of water generated by imidization, the amount of water contained in the reaction solvent, and the amount of simixane bond. Depending on the moisture content, it may not be necessary to add water.

The silylating agent is used to control the molecular weight of the intermediates G to avoid infinite polymerization due to siloxane bonding at their ends. The amount F mol of the silylating agent of formula (9) used is preferably 1 or less as F/(DXk) 1
There is no particular need to add more than that.

If the reaction temperature in the second stage is less than 60°C, the reaction will be slow and it is not practical.In the present invention, an imidization reaction accelerator such as a tertiary amine can be added at a temperature of 60°C or higher. Since the water generated during imidization is immediately consumed in hydrolysis and the direction of the reaction is directed toward imidization, and the imidization reaction proceeds quickly, it is not necessary to add an imidization reaction promoter. Although it is possible to add an acid catalyst or the like to promote the hydrolysis reaction, it is preferable not to add it in consideration of the adverse effects if it remains afterwards.

In the second stage of the reaction, when a silylating agent is used, the imidization reaction and the siloxane bonding reaction proceed smoothly without gelling the reaction solution, and the amount of silylating agent used and the reaction conditions can be controlled. The viscosity of the reaction solution, that is, the molecular weight of the precursor, can be freely controlled by varying each within the above-mentioned ranges.

In this way, the soluble imidosiloxane precursor has an appropriate intrinsic viscosity of 0.05 to 5 dl/f and therefore an appropriate molecular weight, is soluble in a solvent, has an 8-triazine ring, and has an imide bond. is obtained.

In the present invention, the intrinsic viscosity (ηinh) is as defined by the measurement conditions described above, but in more detail, tnη/η0 ηinh■□ (where η is the polymerization solvent using an Ubbelohde viscometer). 0.5% by weight in a solvent with the same composition as that at a temperature of 30±
The value is measured at 0.01"C, η is the measured value of the same solvent at the same temperature using an Ubbelohde viscometer, and C is the concentration of 0.5'l/dl.) It will be done.

If the intrinsic viscosity is less than 0.05 dllI, the coating state of the coating liquid is not good, and therefore the coating film formation is not sufficient.
If it exceeds 5 dl/f, it becomes difficult to dissolve or becomes insoluble, making it impractical.

The degree of imidization can be controlled by the reaction temperature and reaction time in the second step.
Furthermore, the longer the reaction time, the higher the ratio of imide groups to amic acid in the polymer, and if necessary, all of the amide and acid can be converted to imide groups.

C. Effect of the method of the present invention] According to the method of the present invention, in the first step reaction, tetracarboxylic dianhydride, guanamines, diamines, and aminocricone compounds are combined at low temperature to form polyamidecarboxylic acid (with aminocricone compounds bonded to both ends). Intermediate G) is obtained [the following formula q→).

(-NH-R"-NH-CO-R"-CO)-HA1O -NH-R6-8iR78-kXk...aυ (where n is O or a positive integer, t is a positive integer (Other symbols have the same meanings as mentioned above.) By applying this intermediate G to the object to be coated and baking it, the cibolyamide carboxylic acid undergoes dehydration and cyclization to form an imide bond, and at the same time the molecular The terminal hydrolyzable group, XI, undergoes a siloxane condensation reaction to increase its molecular weight to form a tough coating film.

By the way, tetracarboxylic dianhydride and diamine (3)
In the synthesis of polyamide carboxylic acid, which is a common polyimide precursor obtained by reacting with #τ equivalent, part or all of this diamine is converted into guanamines (2
), the molecular weight of the resulting polyamide carboxylic acid decreases as the ratio of guanamines increases, and the viscosity of the solution decreases, and even if you try to bake it after applying it to the object to be coated, it may not have the ability to form a coating. Alternatively, it is difficult to obtain a sufficiently tough coating film.

However, the method of the present invention makes it possible to easily synthesize a useful polyimide precursor having a triazine ring that has many unique physical properties. Next, the two-step reaction begins with a solution t- of intermediate G represented by the formula Qυ.
By heating to 60 to 200°C, part or all of the polyamide carboxylic acid in the Si molecule is dehydrated and cyclized to form an imide bond, and at the same time, the hydrolyzable group at the end of the molecule, Xi, is hydrated by the water etc. produced. It decomposes and becomes high in molecular weight through siloxane condensation.

At this time, if necessary, a silylating agent represented by formula (9) may be added within the range of formula (8) to suppress gelation due to rapid increase in molecular weight.

When a precursor having such an imidized chemical structure is coated on the object to be coated and fired, it is possible to perform the firing at a low temperature, and the heat resistance of the object to be coated is poor.
If it is not expensive, the profit is large.

The thus obtained imidized polyimidosiloxane precursor that has undergone the second reaction has a molecular weight of 0.05 to 5 dl/f in terms of intrinsic viscosity.

C. Method of using the precursor according to the present invention] The polyimidosiloxane precursor according to the present invention (hereinafter sometimes simply referred to as precursor) can be used as a protective material, an insulating material, an adhesive, a material, a film, and a structural material in the field of electronic equipment. It can be widely used as a precursor to give In most cases, it is dissolved in a solvent and used in the form of a solution, such as Fes, so it is preferable to use the solution obtained by the method of the present invention either by concentrating it or diluting it with a solvent. As the solvent, the same solvent as the reaction solvent can be used. For example, when using the precursor solution as an electronic material, ionic substances are removed from the precursor solution using a solid adsorbent, etc., as necessary, and K1
It can be used as a coating solution by removing minute solid impurities using a micrometer or smaller filter. The concentration of this coating solution is determined depending on the required thickness of the coating film, but is preferably 40% by weight or less, and a range of 0.3 to 25% by weight is often preferred in actual use.

The coating solution is uniformly applied to a silicon wafer, glass plate, etc. using a spinner or the like according to a conventional method and baked. The firing conditions vary depending on the solvent used, the thickness of the coating film, the degree of imidization of the precursor, etc., but the firing can be performed at 100 to 250°C for a relatively short time of about 0.5 to 1.5 hours. That's enough. By such calcination, the imidization rate of the precursor whose imidization rate was less than 100% becomes 100%, and the precursor whose molecular weight is not so large and is soluble in the solvent increases crosslinking by siloxane bonds and becomes a solvent-insoluble infinite network structure. However, the transparent light yellow color of the precursor solution turns into a transparent brown color (pale yellow to colorless for thin materials with a thickness of several micrometers or less), forming a very hard and highly heat-resistant film. .

The precursor obtained by the method of the present invention shows good results as a liquid crystal aligning agent.

[Effects of the present invention]

The soluble polyimide siloxane precursor having an 8-triazine ring according to the present invention has an appropriate intrinsic viscosity, so the viscosity of the solution is appropriate and coating can be performed well. The firing conditions can be selected depending on the degree of imidization because the purpose is to imidize the chemical moieties and complete the siloxane condensation reaction at the unreacted active sites. In the case of a completely imidized precursor solution, it is possible to bake at a relatively low temperature of 100 to 150°C,
This can be of great benefit depending on the heat resistance of the object to be coated.

In addition, silicon atoms are present in the precursor molecules, which form si-tetraxane bonds through the reaction and/or calcination in the second step, which makes them a good material for silicon wafers, glasses, etc. containing silicon and silicon compounds. It is thought to provide film-forming ability and adhesion.

Next, in the synthesis of polyimide from guanamines and tetracarboxylic dianhydrides, which are difficult to achieve high molecular weight, by placing an aminocricon compound at both ends, both terminals were activated and high molecular weight was made possible. That's true. By introducing a triazine ring, it becomes possible to significantly improve the stability of a precursor solution that has poor storage stability, and it can be said that this has a great practical effect. Polymers with triazines/rings are generally said to have good properties as insulating materials, such as high insulation, wear resistance, and radiation resistance.
It is naturally expected that the precursor of the present invention will also have these characteristics. Expansion to areas other than electronic materials is a subject for future consideration.

(Examples, Comparative Examples, and Usage Tests) The present invention will be explained in more detail below using Examples, Comparative Examples, and Usage Tests.

Example 1 Eleven flasks equipped with a stirrer, addition funnel, thermometer, condenser and nitrogen purge were fixed in cold water.

After purging the inside of the flask with nitrogen gas, 500 wl of dehydrated and purified N-methyl-2-pyrrolidone, 66.
6Of (0,356 mol) of benzoguanamine was added and the solution was heated to 108.49F while keeping it at 25-30"C.
(0,474 mol) of pyromellitic dianhydride was added in 30 minutes through the addition funnel and kept at this temperature for 1 hour.
The reaction was carried out at 5 to 50°C for 1 hour to obtain a homogeneous liquid. In addition, 50.60 f (0,237 mol) of aminophenyltrimethoxine 2 (2.3% ortho isomer, 6% meta isomer)
(consisting of 1.2% and 36.5% of disparate isomers) was added, and the reaction was carried out at this temperature for 2 hours. This first stage reaction yielded a pale yellow transparent liquid. Next, as a second stage reaction, the temperature of this reaction solution was further raised, and the reaction was carried out at 100°C for 9 hours. As a result, a soluble polyimidosiloxane precursor solution having an s-triazine ring was obtained as a light brown transparent liquid having a rotational viscosity of 54 centivoices at 25°C.

A portion of this precursor solution was taken and dried at room temperature and under reduced pressure to obtain a pale brown solid precursor.

The intrinsic viscosity of this precursor in N-methyl-2-pyrrolidone was 0.0941/f.

Here, rotational viscosity refers to an E-type viscometer (V manufactured by Tokyo Keiki Co., Ltd.).
ISCONICEMD)? This is the viscosity measured at a working temperature of 25°C (the same applies hereinafter).

In addition, Figure 1 shows the infrared absorption spectrum of the first precursor obtained in this example.
It is a vector diagram. In FIG. 1, the absorption spectrum of the imide group (5,63l1m and 18.85μFFJ) is clearly present.

Example 2 22.60f (0,1
21 mol) of benzoguanamine was placed in 500 ml of N-methyl-2-pyrrolidone, and this solution was
s2.6710.2+1 mole)
pyromellitic dianhydride was added over 60 minutes, and the reaction was carried out at this temperature for 1 hour and then at 40 to 50°C for 1 hour to obtain a homogeneous solution. In this, 58.46F (0,241 mol)
3-aminopropyltriethoxysilane was added thereto, and the reaction was carried out at this temperature for 1 hour.

The temperature of the first-stage reaction solution was further raised and the reaction was carried out at 100° C. for 6 hours to carry out the second-stage reaction. As a result, a light brown transparent solution of a soluble polyimidosiloxane precursor having an 8-triazine ring was obtained with a rotational viscosity of 8.3 centivoids at 25°C. The intrinsic viscosity of this precursor was 0.07 dt/f.

According to the infrared absorption spectrum of the precursor obtained in this example, the absorption spectrum of imide groups was clearly present.

Comparative Example 1 59.46F (0,3
18 mol) of benzoguanamine Iso.

wl of N-methyl-2-pyrrolidone, and while keeping this solution fc at 25 to 30°C, 69.291/(0,
318 mol) throat romellitic dianhydride was added over 30 minutes, and the temperature was further raised to 40-45°C for 3 hours at this temperature, and
The reaction was carried out for a period of time to obtain a pale yellow homogeneous solution. After completion of this reaction, the rotational viscosity at 25°C was 7.1 centivoise.

Example 3 32.68F (0,1
75 mol) of benzoguanamine and 34.96 f (0,
175 mol) of 4.41-diaminodiphenyl ether was added to 500 wtl of N-methyl-2-pyrrolidone, and the solution was heated to 101.
5511 (0,466 mol) of pyromellitic dianhydride was added in 30 minutes and kept at this temperature for a further 1 hour.
The reaction was carried out at 5°C for 30 minutes to obtain a homogeneous solution. 51 to this
．． 54F (0,232 mol) of 3-7minoprobyltriethoxysilane and 4.13F (0,0349 mol) of trimethylethoxysilane were added, and the reaction was further carried out at this temperature for 2 hours to obtain a homogeneous solution. Ta. The temperature of this first stage reaction completed liquid was further raised and the reaction was carried out at 100° C. for 8 hours to complete the second stage reaction. As a result, a light brown transparent homogeneous liquid having a rotational viscosity of 230 centivoise at 25°C was obtained. The intrinsic viscosity of this precursor is 0.13 di/I
Met.

According to the infrared absorption spectrum of the precursor obtained in this example, the absorption spectrum of imide groups was clearly present.

Example 4 1.711 (0,01
37 mol) acetoguanamine, 24.34 g (0,1
23 mol) of 4,4'-diaminodiphenylmethane and 1.61 F (0,0136 mol) of trimethylethoxysilane were put into 500 ml of N-methyl-2-pyrrolidone, and the solution was kept at 25-30°C. While 52.
74f (0,164 mol) of benzophenone tetracarboxylic dianhydride was added over 30 minutes, and the reaction was carried out at this temperature for 1 hour and then at 40-45°C for 1 hour to obtain a homogeneous solution. To this, 12.08jF (0,0546 mol) of 3-
Add aminopropyltriethoxysilane to 50-55
The temperature was raised to 0.degree. C., and the reaction was carried out for 1.5 hours to obtain a homogeneous solution. The temperature of this first stage reaction completed liquid was further raised and the reaction was carried out at 120°C for 5 hours to complete the second stage reaction.

As a result, a pale brown homogeneous liquid having a rotational viscosity of 840 centivoids at 25°C was obtained. The intrinsic viscosity of this precursor is 1.2
It was dt/I.

Example 5 29.81F (0,1
59 mol) of benzoguanamine and 17.63y (0,
0,796 mol) of 3-aminopropyltriethoxysilane was added to 500 ml of N-methyl-2-pyrrolidone, and while keeping this solution at 20-25°C, 4-aminopropyltriethoxysilane was added.
8.42 f (0,199 mol) of romellitic dianhydride was added over a period of 30 minutes and kept at this temperature for 2 hours.
The reaction was carried out at ~55°C for 1 hour to obtain a homogeneous liquid. This first
The temperature of the step-reaction completed liquid was further raised and the reaction was carried out at 100° C. for 8 hours to complete the second step reaction. As a result, a light brown transparent liquid having a rotational viscosity of 12 centivoise at 25°C was obtained.

The intrinsic viscosity of this precursor was 0.11 dl/fl.

When this precursor solution was stored at a temperature of 25°C for 60 days, the rotational viscosity at 25°C was 12 centivoise, indicating excellent storage stability.

Comparative Example 2 Using the same equipment and method as in Example 1, 31.18g (0.1
56 mol) of 4,4'-diaminodiphenyl ether,
, 17.24F (0.0779%) of 3-7 minoprobyl triethoxysilane and 8.7711 (0.031%
9 mol) of trimethylethoxysilane' in 1500 r/N-methyl-2-pyrrolidone, and this solution was
42.469 (0,
195% #) of pyromellitic dianhydride was added over 30 minutes, and the reaction was carried out at this temperature for 2 hours and further at 40-45°C for 1 hour to obtain a homogeneous solution.

This first stage reaction completed liquid was further heated to 100°C for 4 hours.
The reaction was carried out for a period of time to complete the second stage reaction. As a result, a light brown transparent liquid having a rotational viscosity of 205 centivoise at 25°C was obtained.

The intrinsic viscosity of this precursor was o, ssd//f.

When this precursor solution was stored at a temperature of 25° C., the viscosity increased over time, and after 34 days the solution gelled and became unusable.

Usage test 1 The following coating and firing test was conducted.

The solution of the polyimide siloxane precursor obtained in each example and the final reaction product solution obtained in Comparative Example 1 were used as coating solutions, and after filtering through a 1 μm filter, they were coated on a spinner Nyotaga 2 plate. Apply and further heat to 150℃,
Baked at 200″C or 250°C for 1 hour to a thickness of 1-2-
After forming a coating film, the condition of the coating film was observed and the results are shown in Table 1.

Table 1 ×The coating film is not formed uniformly.

Usage test 2 The following adhesion test was conducted.

Various coating solutions shown in Table 2 eζ were applied to the surface of a slide glass using a spinner, and each was baked at 150"C, 200°C or 250°C for 1 hour to form a coating film of 1 to 2 μm. Thereafter, the coating solution was heated at 90°C. After processing for 4 hours in a constant temperature and humidity chamber maintained at 95% relative humidity, the resulting coating film was cut into small square pieces of 2H on each side, and cellophane tape was pasted on the surface. It was immediately removed. - Table 2 shows the number of paint film pieces that were peeled off along with the cellophane tape, expressed as a number per 100 before peeling off.

Table 2 * Polyamide carboxylic acid phase, a common polyimide precursor synthesized from pyromellitic dianhydride and 4,4'-diaminodiphenyl ether. The solvent is N-methyl-
It is 2-pyrrolidone, has a solid content concentration of 18% by weight, and a rotational viscosity of 1050 centiboise at 25°C.

From the results in Tables 1 and 2, it is clear that the precursor according to the present invention requires low temperature conditions (150
℃) and for a short time (1 hour), it was found that a coating film with sufficient strength and adhesive strength was formed.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum diagram of the soluble polyimide siloxane precursor having an S-triazine ring according to the present invention obtained in Example 1. that's all

Claims (1)

[Scope of Claims] A mole of tetracarboxylic dianhydride represented by the following formula (1), B mole of guanamine represented by formula (2), E mole of diamine represented by formula (3) and formula (4). ) in the presence of a solvent at 0 to 60°C, with the relationships of formula (5), formula (6), and approximately formula (7) existing between A, B, E, and D. After carrying out the reaction at a temperature of 0.2 to 6 hours, F in the range shown by formula (8)
A silylating agent represented by the formula (9) in moles is added, and 60
React for 0.5 to 30 hours at a temperature of ℃ to 200℃, and make the intrinsic viscosity 0.05 to 5 g/dl measured in a solvent at a temperature of 30 ± 0.01℃ and a concentration of 0.5% by weight. A method for producing an imidized soluble polyimidosiloxane precursor having a characteristic s-triazine ring. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) NH_2-R^2-NH_2...(3) NH_2-R^6 -SiR^7_8_-_kX^1_k
...(4) D/(B+D+E)≧0.1...(5) However, B>0 B/(B+E)≧0.05...(6) 2A=2B+2E+D...(7) 0 ≦F/Dk≦1...(8) R^1^1R^1^2R^1^3SiX^2...(9
) [In formulas (1) to (4) and (9), R^1 represents a tetravalent carbocyclic aromatic group, and R^2 has a carbon number of 2 to 12
aliphatic group with 4 to 30 carbon atoms, alicyclic group with 4 to 30 carbon atoms, 6 carbon atoms
~ Represents 30 aromatic aliphatic groups, carbocyclic aromatic groups having 6 to 30 carbon atoms, or the following formula (10) ▲ Numerical formula, chemical formula,
There are tables, etc. ▼...(10) {However, R^9 is -(CH_2)-_s, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas, chemical formulas , there are tables, etc. ▼ and (
However, here s represents an integer of 1 to 4. ), R^3 and R^4 independently represent an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group having 7 to 12 carbon atoms;
takes a value of 1≦l≦100. }, R^6 is independent of R^9 - (CH_2) -_s, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ mathematical formulas, chemical formulas, tables, etc. There is ▼ (where s indicates an integer from 1 to 4), R^7, R
^1^1, R^1^2 and R^1^3 independently have a carbon number of 1
~6 alkyl group, phenyl group, or alkyl-substituted phenyl group having 7 to 12 carbon atoms, R^1^0 represents an aliphatic group having 8 or less carbon atoms, an araliphatic group, or hydrogen, and X^1 and X^2 independently represent an alkoxy group, an acetoxy group, a halogen or a hydroxyl group, and have a value of 1≦k≦3. ]